CN110504473A - A kind of ion-conductive membranes used for all-vanadium redox flow battery and preparation method thereof - Google Patents
A kind of ion-conductive membranes used for all-vanadium redox flow battery and preparation method thereof Download PDFInfo
- Publication number
- CN110504473A CN110504473A CN201810481700.5A CN201810481700A CN110504473A CN 110504473 A CN110504473 A CN 110504473A CN 201810481700 A CN201810481700 A CN 201810481700A CN 110504473 A CN110504473 A CN 110504473A
- Authority
- CN
- China
- Prior art keywords
- ion
- vanadium redox
- flow battery
- redox flow
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of ion-conductive membranes used for all-vanadium redox flow battery and preparation method thereof, belong to vanadium redox battery (VRB) technical field.With perfluorinated sulfonic resin, Kynoar (PVDF) for raw material, it is dissolved by organic solvent, conducting polymer is added, be uniformly mixed it, homogeneous solution is laid on clean glass plate, cooling obtains composite membrane after held for some time in an oven.The method of the present invention simple process, prepared film high mechanical strength, vanadium ion permeability are low, have good chemistry, thermal stability, cheap, are applicable to vanadium redox battery (VRB).
Description
Technical field
The present invention relates to vanadium redox battery (VRB) technical fields, and in particular to a kind of all-vanadium flow battery
With ion-conductive membranes and preparation method thereof.
Background technique
The new energy such as exploitation wind energy, solar energy are the important channels for solving energy resources shortage, represent energy future hair
The direction of exhibition.But it is limited by time and region dependence, off-grid wind energy, solar power generation must use energy-storage system, otherwise
It is difficult round-the-clock utilization；And direct grid-connected also must carry out peak regulation and frequency modulation to power grid using energy-storage system, it otherwise can be to power grid
Power and frequency band carry out biggish impact.Therefore efficient, large-scale energy storage technologies just become the key of its development and application
Core.
Vanadium cell (vanadium oxide reduction flow battery/Vanadium redox flow battery) is based on VO2+/VO2 +
With V2+/V3+The liquid flow energy storage battery technology of electricity pair, energy stores are in electrolyte.Compared with traditional battery, vanadium cell can
High current fast charging and discharging, self-discharge rate are low, realize the massive store of energy, are to meet smart grid and wind energy, the sun
The ideal stored energy form that can be generated electricity to extensive energy storage demand.China's vanadium resource advantage abundant is also to develop vanadium cell energy storage skill
Art provides condition.
Vanadium redox battery is with V (II)/V (III) and V (IV)/V (V) oxidation-reduction pair H2SO4It is molten
Liquid makees positive and negative half-cell electrolytes respectively.H2SO4It is ionized into H+And SO4 2-, then H in electrolyte+Persistently instead of ion exchange
H in film+, and enter in another room electrolyte, complete conducting process.Upon discharging, the VO in anode electrolyte2 +Ion
It is reduced to VO2+Ion, the V in electrolyte liquid2+Ion is oxidized to V3+Ion.When charging, process is just opposite.
Vanadium battery electrode reaction is as follows:
Anode:
Cathode:
Vanadium cell develops to today, has reached a more advanced level, but still there are many critical issue is urgent
It needs to solve, wherein key material diaphragm is exactly one of them.Vanadium cell septation has isolation positive and negative electrode electrolyte molten
Liquid, the effect for preventing different valence state vanadium ion from interpenetrating prevent the cross contamination of positive and negative electrode electrolyte from improving ion selection
Property, proton can pass freely through, have to the vanadium of different valence state highly selective.Currently, Nafion series membranes are mainly used both at home and abroad,
But its resistance vanadium performance is poor, and self-discharge of battery phenomenon is more significant, and fancy price is but also the cost of vanadium cell is high.
Therefore, it develops the diaphragm that one kind is cheap, resistance vanadium is good and very important effect is played to the commercial applications of vanadium cell.
Summary of the invention:
In order to solve, vanadium ion transmitance existing for perfluorosulfonic acid proton exchange film used at present is high, expensive etc. asks
Topic, the object of the present invention is to provide a kind of ion-conductive membranes used for all-vanadium redox flow battery and preparation method thereof, prepare ionic conduction
The ion-selective permeability of film is good and cost substantially reduces, and is applicable to vanadium redox battery (VRB).
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of preparation method of ion-conductive membranes used for all-vanadium redox flow battery, this method comprises the following steps:
(1) PVDF resin (Kynoar) being added in organic solvent, heating stirring dissolves under the conditions of 60~80 DEG C,
It is made into PVDF resin solution；
(2) perfluorinated sulfonic resin is added in organic solvent, dissolves by heating 4h under the conditions of 200~240 DEG C, is made into perfluor
Sulfonic acid solutions；
(3) the perfluorinated sulfonic acid solution in the PVDF resin solution and step (2) in step (1) is mixed, and stirred for 24 hours,
Obtain mixed solution；
(4) it takes a certain amount of conducting polymer to be added in mixed solution obtained by step (3), it is molten to obtain film forming after mixing evenly
Liquid；
(5) solution casting method is used, on a glass by the casting of film forming solution obtained by step (4), after carrying out isothermal holding
Obtain the ion-conductive membranes used for all-vanadium redox flow battery.
In above-mentioned steps (1), in the PVDF resin solution concentration of PVDF resin (Kynoar) be 3~
15wt.%.The molecular formula of Kynoar is as follows:
[-CH2-CF2-]n
In above-mentioned steps (2), the concentration of perfluorinated sulfonic resin is 5~20wt.% in the perfluorinated sulfonic acid solution.Perfluor sulphur
The molecular formula of acid resin is as follows:
Organic solvent described in above-mentioned steps (1) and step (2) is dimethylbenzene, N,N-dimethylformamide, N, N- diformazan
Base second formamide, dimethyl sulfoxide or N- base pyrrolidones.
In above-mentioned steps (3), the weight ratio of PVDF resin and perfluorinated sulfonic resin is 1:(0.5 in the mixed solution
~10).
In above-mentioned steps (4), the conducting polymer is polyaniline or polypyrrole.
In above-mentioned steps (4), the ratio of the conducting polymer and mixed solution is 1:(20~100).
In above-mentioned steps (5), the process of the solution casting method are as follows: the film forming solution is equably laid in cleaning
On glass plate, the organic solvent volatilization in 100 DEG C of heat preservation 4h, insulating process in film forming solution in an oven；Temperature fall again
After obtain composite membrane, the as described ion-conductive membranes used for all-vanadium redox flow battery.
It advantages of the present invention and has the beneficial effect that:
(1) conducting polymer is to make it by insulating through chemistry or electrochemical doping method by the macromolecule with conjugatedπbond
Body is changed into a kind of high molecular material of conductor, and high conductivity polymerize by the conductive characteristic with metal and semiconductor, the present invention
Object material is introduced into film, improve film electric conductivity simultaneously, reduce film vanadium ion permeability.
(2) PVDF is a kind of thermoplastic resin, is linear crystalline polymer, since the combination of fluorocarbon chain can be high, so
With good heat-resisting, corrosion resistance, chemical stability, its tensile strength is higher in fluoroplastics, its decomposition
Temperature is up to 316 DEG C.The PVDF that the present invention selects chemical stability good, which is added in perfluoro sulfonic acid membrane, reduces the molten of perfluoro sulfonic acid membrane
It is swollen, reduce vanadium ion infiltration；Reduce the dosage of perfluorinated sulfonic resin simultaneously, reduces diaphragm cost.Therefore, prepared by the present invention multiple
Closing film has good resistance vanadium performance, mechanical performance, chemical stability and high conductivity, and substantially reduces production cost, can
It is widely used in vanadium redox battery field.
Specific embodiment
Below by embodiment, technical scheme of the present invention will be further explained in detail.
Embodiment 1:
In the present embodiment, the specific steps are as follows:
(1) 7.5gPVDF resin is dissolved in dimethyl acetamide, heating stirring dissolves 5h in 80 DEG C, is made into quality hundred
The PVDF resin solution that score is 10%.
(2) 5g perfluorinated sulfonic resin is dissolved in dimethylformamide, dissolves by heating 4h in 240 DEG C, be made into quality hundred
The PVDF perfluorinated sulfonic acid solution that score is 15%.
(3) the perfluorinated sulfonic acid solution in the PVDF solution and 15ml step (2) in 20ml step (1) is taken to be mixed for 24 hours.
(4) it takes 0.1g polyaniline to be added in the mixed solution in step (3), continues to stir 5h, obtain film forming solution.
(5) solution casting method is used, it is on a glass by the film forming solution casting of step (4), dry at a temperature of 100 DEG C
4h volatilization film forming, film with a thickness of 50 μm.
The correlated performance data of the present embodiment is as follows:
Diaphragm assembling single group battery manufactured in the present embodiment carries out charge and discharge cycles, and the coulombic efficiency of battery is 95%, electricity
Pressing efficiency is 74%, energy efficiency 70.3%, tensile strength 18MPa.
Embodiment 2:
In the present embodiment, the specific steps are as follows:
(1) 7.5gPVDF resin is dissolved in dimethyl acetamide, heating stirring dissolves 5h in 80 DEG C, is made into quality hundred
The PVDF resin solution that score is 10%.
(2) 5g perfluorinated sulfonic resin is dissolved in dimethylformamide, dissolves by heating 4h in 240 DEG C, be made into quality hundred
The PVDF perfluorinated sulfonic acid solution that score is 15%.
(3) the perfluorinated sulfonic acid solution in the PVDF solution and 25ml step (2) in 10ml step (1) is taken to be mixed for 24 hours.
(4) it takes 0.1g polyaniline to be added in the mixed solution in step (3), continues to stir 5h, obtain film forming solution.
(5) solution casting method is used, it is on a glass by the film forming solution casting of step (4), dry at a temperature of 100 DEG C
4h volatilization film forming, film with a thickness of 50 μm.
The correlated performance data of the present embodiment is as follows:
Diaphragm assembling single group battery manufactured in the present embodiment carries out charge and discharge cycles, and the coulombic efficiency of battery is 93%, electricity
Pressing efficiency is 77%, energy efficiency 71.6%, tensile strength 17MPa.
Embodiment 3:
In the present embodiment, the specific steps are as follows:
(1) 7.5gPVDF resin is dissolved in dimethyl acetamide, heating stirring dissolves 5h in 80 DEG C, is made into quality hundred
The PVDF resin solution that score is 10%.
(2) 5g perfluorinated sulfonic resin is dissolved in dimethylformamide, dissolves by heating 4h in 240 DEG C, be made into quality hundred
The PVDF perfluorinated sulfonic acid solution that score is 15%.
(3) the perfluorinated sulfonic acid solution in the PVDF solution and 7.5ml step (2) in 25ml step (1) is taken to be mixed
24h。
(4) it takes 0.1g polyaniline to be added in the mixed solution in step (3), continues to stir 5h, obtain film forming solution.
(5) solution casting method is used, it is on a glass by the film forming solution casting of step (4), dry at a temperature of 100 DEG C
4h volatilization film forming, film with a thickness of 50 μm.
The correlated performance data of the present embodiment is as follows:
Diaphragm assembling single group battery manufactured in the present embodiment carries out charge and discharge cycles, and the coulombic efficiency of battery is 96%, electricity
Pressing efficiency is 70%, energy efficiency 67%, tensile strength 20MPa.
Embodiment 4:
In the present embodiment, the specific steps are as follows:
(1) 7.5gPVDF resin is dissolved in dimethyl acetamide, heating stirring dissolves 5h in 80 DEG C, is made into quality hundred
The PVDF resin solution that score is 10%.
(2) 5g perfluorinated sulfonic resin is dissolved in dimethylformamide, dissolves by heating 4h in 240 DEG C, be made into quality hundred
The PVDF perfluorinated sulfonic acid solution that score is 15%.
(3) the perfluorinated sulfonic acid solution in the PVDF solution and 25ml step (2) in 10ml step (1) is taken to be mixed for 24 hours.
(4) it takes 0.5g polyaniline to be added in the mixed solution in step (3), continues to stir 5h, obtain film forming solution.
(5) solution casting method is used, it is on a glass by the film forming solution casting of step (4), dry at a temperature of 100 DEG C
4h volatilization film forming, film with a thickness of 50 μm.
The correlated performance data of the present embodiment is as follows:
Diaphragm assembling single group battery manufactured in the present embodiment carries out charge and discharge cycles, and the coulombic efficiency of battery is 96%, electricity
Pressing efficiency is 75%, energy efficiency 72%, tensile strength 13MPa.
Comparative example 1:
In the present embodiment, the specific steps are as follows:
(1) 7.5gPVDF resin is dissolved in dimethyl acetamide, heating stirring dissolves 5h in 80 DEG C, is made into quality hundred
The PVDF resin solution that score is 10%.
(2) 5g perfluorinated sulfonic resin is dissolved in dimethylformamide, dissolves by heating 4h in 240 DEG C, be made into quality hundred
The PVDF perfluorinated sulfonic acid solution that score is 15%.
(3) the perfluorinated sulfonic acid solution in the PVDF solution and 25ml step (2) in 10ml step (1) is taken to be mixed for 24 hours.
(4) it takes 1g polyaniline to be added in the mixed solution in step (3), continues to stir 5h, obtain film forming solution.
(5) solution casting method is used, it is on a glass by the film forming solution casting of step (4), dry at a temperature of 100 DEG C
4h volatilization film forming, film with a thickness of 50 μm.
The correlated performance data of the present embodiment is as follows:
Diaphragm film forming manufactured in the present embodiment is poor, tensile strength 7MPa.
The results showed that by adjusting the ratio of Kynoar and perfluorinated sulfonic resin, the electric current of its film after tested
Efficiency and voltage efficiency change；Therefore the comprehensive performance of film improves.Composite diaphragm electric conductivity prepared by the present invention meets
Vanadium cell requirement, while having many advantages, such as good resistance vanadium performance and chemical stability, and cheap, it can be wide
It is applied to vanadium redox battery field generally.
Claims (9)
1. a kind of preparation method of ion-conductive membranes used for all-vanadium redox flow battery, it is characterised in that: this method comprises the following steps:
(1) PVDF resin is added in organic solvent, heating stirring dissolves under the conditions of 60~80 DEG C, and it is molten to be made into PVDF resin
Liquid；
(2) perfluorinated sulfonic resin is added in organic solvent, dissolves by heating 4h under the conditions of 200~240 DEG C, is made into perfluorinated sulfonic acid
Solution；
(3) the perfluorinated sulfonic acid solution in the PVDF resin solution and step (2) in step (1) is mixed, and stirred for 24 hours, obtained
Mixed solution；
(4) it takes a certain amount of conducting polymer to be added in mixed solution obtained by step (3), obtains film forming solution after mixing evenly；
(5) solution casting method is used, on a glass by the casting of film forming solution obtained by step (4), is obtained after carrying out isothermal holding
Obtain the ion-conductive membranes used for all-vanadium redox flow battery.
2. the preparation method of ion-conductive membranes used for all-vanadium redox flow battery according to claim 1, it is characterised in that: step
(1) in, the concentration of PVDF resin is 3~15wt.% in the PVDF resin solution.
3. the preparation method of ion-conductive membranes used for all-vanadium redox flow battery according to claim 1, it is characterised in that: step
(2) in, the concentration of perfluorinated sulfonic resin is 5~20wt.% in the perfluorinated sulfonic acid solution.
4. the preparation method of ion-conductive membranes used for all-vanadium redox flow battery according to claim 1, it is characterised in that: described to have
Solvent is dimethylbenzene, N,N-dimethylformamide, N, N- dimethyl second formamide, dimethyl sulfoxide or N- base pyrrolidones.
5. the preparation method of ion-conductive membranes used for all-vanadium redox flow battery according to claim 1, it is characterised in that: step
(3) in, the weight ratio of PVDF resin and perfluorinated sulfonic resin is 1:(0.5~10 in the mixed solution).
6. the preparation method of ion-conductive membranes used for all-vanadium redox flow battery according to claim 1, it is characterised in that: step
(4) in, the conducting polymer is polyaniline or polypyrrole.
7. the preparation method of ion-conductive membranes used for all-vanadium redox flow battery according to claim 1 or 5, it is characterised in that: step
Suddenly in (4), the ratio of the conducting polymer and mixed solution is 1:(20~100).
8. the preparation method of ion-conductive membranes used for all-vanadium redox flow battery according to claim 1, it is characterised in that: step
(5) in, the process of the solution casting method are as follows: be equably laid in the film forming solution on clean glass plate, in baking oven
In in 100 DEG C of heat preservation 4h, insulating process in film forming solution organic solvent volatilization；Composite membrane is obtained after Temperature fall again, i.e.,
For the ion-conductive membranes used for all-vanadium redox flow battery.
9. a kind of ion-conductive membranes used for all-vanadium redox flow battery prepared using claim 1 the method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810481700.5A CN110504473A (en) | 2018-05-18 | 2018-05-18 | A kind of ion-conductive membranes used for all-vanadium redox flow battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810481700.5A CN110504473A (en) | 2018-05-18 | 2018-05-18 | A kind of ion-conductive membranes used for all-vanadium redox flow battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110504473A true CN110504473A (en) | 2019-11-26 |
Family
ID=68584023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810481700.5A Pending CN110504473A (en) | 2018-05-18 | 2018-05-18 | A kind of ion-conductive membranes used for all-vanadium redox flow battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110504473A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111395008A (en) * | 2020-03-26 | 2020-07-10 | 中国科学院金属研究所 | Perfluorosulfonic acid resin/polyvinylidene fluoride composite electrospun membrane and preparation method thereof |
| CN115536884A (en) * | 2022-11-25 | 2022-12-30 | 杭州德海艾科能源科技有限公司 | Modified composite membrane for vanadium redox flow battery and preparation method thereof |
| CN117913331A (en) * | 2024-03-14 | 2024-04-19 | 中海储能科技(北京)有限公司 | Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103268925A (en) * | 2013-05-28 | 2013-08-28 | 严川伟 | Preparation process of perfluoro-sulfonate ion-exchanged membrane for vanadium battery |
| CN103996865A (en) * | 2013-02-19 | 2014-08-20 | 中国科学院上海有机化学研究所 | High methanol resistant polymer electrolyte membrane and preparation method thereof |
| CN106602102A (en) * | 2015-10-19 | 2017-04-26 | 中国科学院金属研究所 | Preparation process of blended membrane for all-vanadium redox flow battery |
| CN107658478A (en) * | 2017-09-22 | 2018-02-02 | 北京协同创新研究院 | A kind of all-vanadium flow battery barrier film and preparation method thereof |
-
2018
- 2018-05-18 CN CN201810481700.5A patent/CN110504473A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996865A (en) * | 2013-02-19 | 2014-08-20 | 中国科学院上海有机化学研究所 | High methanol resistant polymer electrolyte membrane and preparation method thereof |
| CN103268925A (en) * | 2013-05-28 | 2013-08-28 | 严川伟 | Preparation process of perfluoro-sulfonate ion-exchanged membrane for vanadium battery |
| CN106602102A (en) * | 2015-10-19 | 2017-04-26 | 中国科学院金属研究所 | Preparation process of blended membrane for all-vanadium redox flow battery |
| CN107658478A (en) * | 2017-09-22 | 2018-02-02 | 北京协同创新研究院 | A kind of all-vanadium flow battery barrier film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIE ZENG等: "Studies on polypyrrole modified nafion membrane for vanadium redox flow battery", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111395008A (en) * | 2020-03-26 | 2020-07-10 | 中国科学院金属研究所 | Perfluorosulfonic acid resin/polyvinylidene fluoride composite electrospun membrane and preparation method thereof |
| CN111395008B (en) * | 2020-03-26 | 2021-10-08 | 中国科学院金属研究所 | Perfluorosulfonic acid resin/polyvinylidene fluoride composite electrospun membrane and preparation method thereof |
| CN115536884A (en) * | 2022-11-25 | 2022-12-30 | 杭州德海艾科能源科技有限公司 | Modified composite membrane for vanadium redox flow battery and preparation method thereof |
| CN115536884B (en) * | 2022-11-25 | 2023-03-10 | 杭州德海艾科能源科技有限公司 | Modified composite membrane for vanadium redox flow battery and preparation method thereof |
| CN117913331A (en) * | 2024-03-14 | 2024-04-19 | 中海储能科技(北京)有限公司 | Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106058313B (en) | Polymer electrolyte, preparation method, polymer dielectric film and all solid state lithium ion secondary cell | |
| CN103219532B (en) | Flow battery sulfonated polyether-ether-ketone base blend ion exchange membrane and preparation method thereof | |
| CN101475699B (en) | Preparation of proton conduction membrane | |
| CN111509278A (en) | Method for recovering capacity and efficiency of all-vanadium redox flow battery on line | |
| CN102610862A (en) | Preparation method for lithium battery taking polypyrrole-coated magnesium borate as anode material | |
| CN102237534A (en) | Perfluorinated sulfonic acid ion exchange membrane preparation process for vanadium redox battery | |
| CN101814605B (en) | Preparation method of fluororesin-containing conductive plastic bi-polar plate | |
| CN110350223B (en) | Nano intercalation internal selection SPEEK/GO/TiO2Preparation method of composite ion selective membrane | |
| CN109810435B (en) | Preparation method of phosphoric acid doped graphene oxide and polyvinylidene fluoride composite membrane | |
| CN110504473A (en) | A kind of ion-conductive membranes used for all-vanadium redox flow battery and preparation method thereof | |
| CN109244537A (en) | Composite solid electrolyte, preparation method and its application | |
| CN108110324A (en) | A kind of preparation method of solid lithium ion battery | |
| CN111446448A (en) | Preparation method of polyimide/graphene composite lithium ion battery cathode material based on conjugated carbonyl | |
| CN108878933B (en) | Preparation method of Nafion/lignin composite proton exchange membrane | |
| CN106549178B (en) | A kind of organic flow battery | |
| Zhang et al. | Manganese species in methane sulfonic acid as the solvent for zinc-manganese redox battery | |
| CN109346729B (en) | Water system semi-flow battery | |
| CN113206283A (en) | Aqueous zinc ion battery electrolyte based on eutectic salt electrolyte | |
| CN110120532A (en) | A kind of preparation method of composite membrane | |
| CN102637891A (en) | Vanadium cell nafion proton membrane and preparation method thereof | |
| CN108075091B (en) | A kind of preparation method of functional porous polyvinylidene fluoride film used for all-vanadium redox flow battery | |
| CN108123155A (en) | A kind of preparation method of non-fluorine porous composite film used for all-vanadium redox flow battery | |
| CN104752737A (en) | Preparation method of novel all-vanadium redox flow battery ion exchange membrane | |
| CN110120540A (en) | A kind of continuous preparation method of porous composite ionic membrane | |
| CN107546399B (en) | Ion exchange membrane with main chain separated from ion exchange group and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191126 |